CN107746258A - A kind of ultralow line changes unburned air brick and its preparation method and application - Google Patents

A kind of ultralow line changes unburned air brick and its preparation method and application Download PDF

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CN107746258A
CN107746258A CN201711054218.5A CN201711054218A CN107746258A CN 107746258 A CN107746258 A CN 107746258A CN 201711054218 A CN201711054218 A CN 201711054218A CN 107746258 A CN107746258 A CN 107746258A
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air brick
content
unburned air
changes
ultralow
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CN107746258B (en
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陈晓林
栾舰
王春艳
王英姿
尹延琪
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Yingkou Four Link High Temperature New Mstar Technology Ltd
University of Science and Technology Liaoning USTL
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Yingkou Four Link High Temperature New Mstar Technology Ltd
University of Science and Technology Liaoning USTL
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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Abstract

The present invention relates to a kind of ultralow line to change unburned air brick and its preparation method and application.Air brick is mixed by intermixture and additive, and described intermixture is by sintering plate corundum particle, aluminium riched spinel particle, corundum fine powder, aluminium riched spinel micro mist, alpha-aluminium oxide micro mist, chrome oxide green fine powder, powdered zirconium oxide and pure calcium aluminate cement composition.Described additive disperses water reducer by heat stabilizer, polycarboxylic acids and mineralizer forms.The present invention offsets caused volume contraction in sintering process using chrome oxide green during use with volumetric expansion caused by the solid solution reaction and pure calcium aluminate cement of corundum phase and the chemical reaction of corundum phase, recycle the transformation toughening effect of zirconium oxide during the course of the reaction, it is+0.01~+0.04% that the ultralow line prepared, which changes unburned air brick to heat permanent Linear change rate, effectively improve Air permenbility and blow out effect, meanwhile the anti-erosion of air brick, thermal shock resistance are superior to like product.

Description

A kind of ultralow line changes unburned air brick and its preparation method and application
Technical field
The present invention relates to technical field of refractory materials, and in particular to a kind of ultralow line changes unburned air brick and its preparation side Method and application.
Background technology
In recent years, furnace outer refining technology turns into indispensable important step in modern steel production, in increase steel Material kind, improve steel product quality etc., increasingly show its superiority.External refining uses BOTTOM ARGON BLOWING technology, can uniform steel Water constituent and temperature, promote the physical-chemical reaction of liquid steel refining.Air brick is most important function element in bottom argon blowing technology, Smooth implementation of its performance to bottom argon blowing technology, ensures that the reliability of furnace outer refining process and security are most important. With the continuous growth of clean steel and high-quality steel demand, the increase of external refining ratio, time lengthening, the work that air brick is born Make load increasing, use condition is increasingly harsh.The volume stability of air brick be weigh its quality an important indicator, slit The bar of formula air brick stitches narrow, generally 200um or so, if air brick burn till or use during Volume Changes compared with Greatly, it will influence the size of slit, too small or excessive slit width can all cause Air permenbility not enough or ooze steel to blow not open, finally Influence Air permenbility and blow out effect.
At present, the material of existing air brick mainly has magnalium chromium matter, chrome corundum, corundum-spinel etc..Pink fused alumina Brick uses material as traditional air brick of steel ladle, and very important effect is served within a very long time, but due to passing The deficiency of the chrome corundum brick of system performance in terms of anti-thermal shock, is easily cracked in use, molten steel is very easy to edge The air flue intrusion brick body cracked, forms molten steel infiltration, and serious will influence Argon effect.In addition, chrome corundum brick is using Afterwards, Cr in brick3+It is oxidized to Cr6+, Cr6+With toxic, environmental pollution can be brought.Therefore, the use of chrome corundum air brick by Limitation is arrived.Corundum-spinel air brick has that corrosion resistance is good, and thermal shock resistance well waits premium properties, can be at utmost Meet the requirement of air brick, but in order to obtain stable volume stability, it, which is prepared, all needs through 1500 DEG C of even more highs Temperature is burnt till obtained, and energy consumption is big, therefore product cost is higher.Existing air brick, or preparation, energy consumption need to be burnt till by high temperature Greatly, product cost is high, or Linear change rate is big in use for unburned air brick, and volume stability is poor.
The content of the invention
An object of the present invention is to provide a kind of ultralow line and changes unburned air brick, and the air brick of preparation burns without high temperature Into under conditions of use, heating permanent Linear change rate between+0.01~+0.04%.It ensure that the Air permenbility of air brick and blow Into effect.Meanwhile the anti-erosion of air brick, thermal shock resistance are superior to like product, alternative existing air brick is in purified steel Wrap and widely use.
The second object of the present invention is to provide the preparation method that a kind of ultralow line changes unburned air brick.
The third object of the present invention is to provide ultralow line and changes application of the unburned air brick in refining ladle air brick.
The technical solution adopted by the present invention is：A kind of ultralow line changes unburned air brick, is mixed by intermixture and additive It is made；
Described intermixture forms as follows by weight percentage：
Described additive disperses water reducer by heat stabilizer, polycarboxylic acids and mineralizer forms, described heat stabilizer Addition is 0.01~0.03wt% of intermixture weight, and the addition that described polycarboxylic acids disperses water reducer is intermixture weight 0.04~0.15wt%, the addition of described mineralizer is 0.01~0.03wt% of intermixture weight.
Preferably, described sintering plate corundum particle, Al2O3Content >=98wt%, bulk density >=3.55g/cm3, Granularity≤8mm, closed porosity 10~20%, 3~10um of aperture.
Preferably, described aluminium riched spinel particle, MgO content 20~26wt%, Al2O372~79wt% of content, Percentage by weight≤2% of impurity content, granularity≤8mm.
Preferably, described corundum fine powder, Al2O3Content >=98wt%, granularity≤0.088mm.
Preferably, in described aluminium riched spinel micro mist, MgO content 20~26wt%, Al2O3Content 72~ 79wt%, percentage by weight≤2% of impurity content, meso-position radius D50 are 5~20um.
Preferably, described active alpha-alumina powder, Al2O3Content >=98wt%, meso-position radius D50 is 0.5~6um.
Preferably, described chrome oxide green fine powder, Cr2O3Content >=98wt%, granularity≤0.044mm.
Preferably, described powdered zirconium oxide, ZrO2Content >=90wt%, granularity≤0.044mm.
Preferably, described pure calcium aluminate cement, Al2O3Content 68~71wt%, CaO 29~32wt% of content, Granularity≤0.044mm.
Preferably, described heat stabilizer is that the one or two or more kinds of of SIS resins, C5 Petropols or calcium carbonate mix Close；It is sodium gluconate, lauryl sodium sulfate (K12), α-sodium olefin sulfonate (AOS) that described polycarboxylic acids, which disperses water reducer, One or two or more kinds of mixing；Described mineralizer is the one or two or more kinds of of yittrium oxide, cerium oxide or nitroglycerin Mixing.
A kind of above-mentioned ultralow line changes the preparation method of unburned air brick, comprises the following steps：
1) stocked up by above-mentioned proportioning；
2) first by corundum fine powder, aluminium riched spinel micro mist, aluminous cement, powdered zirconium oxide, active alpha-alumina powder, Polycarboxylic acids disperses water reducer and chrome oxide green fine powder mixes 3~5 minutes in premixing machine, obtains premixing flour, standby；
3) heat stabilizer and mineralizer are taken, heat stabilizer and the water of mineralizer gross weight 3~4% is added, stirs, it is standby With；
4) sintering plate corundum particle and aluminium riched spinel particle are put into batch mixer, then addition step 2) obtains pre- Mixed powder, dry-mixed 1~3 minute, is eventually adding the compound that step 3) obtains, and uniformly mixes 3~8 minutes, obtains castable；
5) castable for obtaining step 4) is added in mould, vibration moulding, and 12~48 are conserved under the conditions of 20~100 DEG C Hour, obtain base substrate；
6) base substrate after step 5) is molded is stripped, and is conserved 72~240 hours under the conditions of 20~100 DEG C, is obtained sample；
7) sample that step 6) obtains is heat-treated 12~48 hours under the conditions of 450~800 DEG C, a kind of ultralow line is made Change unburned air brick.
The present invention, sintering plate corundum granularity are less than 8mm, principal crystalline phase corundum phase, crystalline size ＞ 40um, transgranular a large amount of envelopes Hold one's breath hole, closed porosity 10~20%, 3~10um of aperture, there is fusing point is high, and corrosion resistance is strong, and thermal shock resistance is excellent etc. Feature.
The present invention, aluminium riched spinel granularity are less than 8mm, principal crystalline phase magnesium aluminate spinel phase, isometric system, crystalline size ＞ 80um, there is the features such as fusing point is high, and corrosion resistance is strong, and thermal shock resistance is excellent.
The present invention, corundum fine powder principal crystalline phase are corundum phase, granularity≤0.088mm, have corrosion resistance good characteristics.
The present invention, active alpha-alumina powder principal crystalline phase are corundum phase, and meso-position radius D50 is 0.5~6um, and there is reaction to live The characteristics of property is high.
The present invention, the ZrO in powdered zirconium oxide2Percentage by weight >=90wt% of content, principal crystalline phase are monoclinic zirconia And cubic zirconia, granularity≤0.044mm.
The present invention, in pure calcium aluminate cement, Al2O368~71wt% of percentage by weight of content, the weight hundred of CaO content Divide 29~32wt% of ratio, principal crystalline phase CA2Phase, hydration rate is slow, and later strength is big, and refractoriness is high, granularity≤0.044mm.
The beneficial effects of the invention are as follows：A kind of ultralow line of the present invention changes unburned air brick, with sintering plate corundum and Aluminium riched spinel is as main material, addition Alpha-alumina, chrome oxide green and partially stabilized zirconia micro mist, using pure calcium aluminate For bonding agent, additional heat stabilizer, water reducer and organic mineralizer, it is made through Low Temperature Heat Treatment.Using being aoxidized during use Volumetric expansion caused by the chemical reaction of the solid solution reaction of chrome green micro mist and corundum phase, pure calcium aluminate cement and corundum phase is offset Caused volume contraction in sintering process, to control the volume stability during air brick use, improve Air permenbility and blow out Effect, the transformation toughening effect of PSZ micro mist during the course of the reaction is recycled, increase the toughness of air brick, improve The thermal shock resistance of air brick.
Embodiment
With reference to embodiment, the invention will be further described.
A kind of ultralow line changes unburned air brick, is mixed by intermixture and additive；
Described intermixture forms as follows by weight percentage：
Described additive disperses water reducer by heat stabilizer, polycarboxylic acids and mineralizer forms.
Above-mentioned intermixture component is added up to 100%, the addition of additive is the percentage amounts of intermixture gross weight, specifically For：The addition of described heat stabilizer is 0.01~0.03wt% of intermixture gross weight, and described polycarboxylic acids disperses diminishing The addition of agent is 0.04~0.15wt% of intermixture gross weight, and the addition of described mineralizer is intermixture gross weight 0.01~0.03wt%.
Described sintering plate corundum particle, Al2O3Content >=98wt%, bulk density >=3.55g/cm3, granularity ≤ 8mm, closed porosity 10~20%, 3~10um of aperture.
Preferably, described aluminium riched spinel particle, MgO content 20~26wt%, Al2O372~79wt% of content, Percentage by weight≤2% of impurity content, granularity≤8mm.
Preferably, described corundum fine powder, Al2O3Content >=98wt%, granularity≤0.088mm.
Preferably, in described aluminium riched spinel micro mist, MgO content 20~26wt%, Al2O3Content 72~ 79wt%, percentage by weight≤2% of impurity content, meso-position radius D50 are 5~20um.
Preferably, described active alpha-alumina powder, Al2O3Content >=98wt%, meso-position radius D50 is 0.5~6um.
Preferably, described chrome oxide green fine powder, Cr2O3Content >=98wt%, granularity≤0.044mm.
Preferably, described powdered zirconium oxide, ZrO2Content >=90wt%, granularity≤0.044mm.
Preferably, described pure calcium aluminate cement, Al2O3Content 68~71wt%, CaO 29~32wt% of content, Granularity≤0.044mm.
Preferably, described heat stabilizer is that the one or two or more kinds of of SIS resins, C5 Petropols or calcium carbonate mix Close；It is sodium gluconate, lauryl sodium sulfate (K12), α-sodium olefin sulfonate (AOS) that described polycarboxylic acids, which disperses water reducer, One or two or more kinds of mixing；Described mineralizer is the one or two or more kinds of of yittrium oxide, cerium oxide or nitroglycerin Mixing.
A kind of above-mentioned ultralow line changes the preparation method of unburned air brick, comprises the following steps：
1) stocked up by above-mentioned proportioning；
2) it is first that corundum fine powder, aluminium riched spinel micro mist, pure calcium aluminate cement, powdered zirconium oxide, active Alpha-alumina is micro- Powder, polycarboxylic acids disperse water reducer and chrome oxide green fine powder mixes 3~5 minutes in premixing machine, obtains premixing flour, standby；
3) heat stabilizer and mineralizer are taken, heat stabilizer and the water of mineralizer gross weight 3~4% is added, stirs, it is standby With；
4) sintering plate corundum particle and aluminium riched spinel particle are put into batch mixer, then addition step 2) obtains pre- Mixed powder, dry-mixed 1~3 minute, is eventually adding the compound that step 3) obtains, uniform wet mixing 3~8 minutes, obtains castable；
5) castable for obtaining step 4) is added in mould, vibration moulding, and 12~48 are conserved under the conditions of 20~100 DEG C Hour, obtain base substrate；
6) base substrate after step 5) is molded is stripped, and is conserved 72~240 hours under the conditions of 20~100 DEG C, is obtained sample；
7) sample that step 6) obtains is heat-treated 12~48 hours under the conditions of 450~800 DEG C, a kind of ultralow line is made Change unburned air brick.
Embodiment 1-6
(1) ultralow line changes the composition such as table 1 of unburned each raw material of air brick
Table 1
(2) ultralow line changes the formula such as table 2 of unburned air brick
Table 2
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Sintering plate corundum particle 30% 35% 40% 45% 50% 55%
Aluminium riched spinel particle 25% 23% 19% 16% 13% 10%
Corundum fine powder 13% 15% 17% 19% 20% 22%
Aluminium riched spinel micro mist 16% 14% 12% 10% 8% 6%
Active alpha-alumina powder 8% 6% 5.5% 4% 3.5% 2%
Chrome oxide green fine powder 1% 1.5% 2% 2.5% 3% 3.5%
Powdered zirconium oxide 3% 2.5% 2% 1.5% 1% 0.5%
Pure calcium aluminate cement 4% 3% 2.5% 2% 1.5% 1%
Heat stabilizer 0.01% 0.02% 0.02% 0.01% 0.02% 0.03%
Polycarboxylic acids disperses water reducer 0.04% 0.06% 0.08% 0.10% 0.12% 0.15%
Organic mineralizer 0.01% 0.02% 0.02% 0.03% 0.02% 0.03%
(3) the parameter such as table 3 that ultralow line changes in the specific preparation method of unburned air brick
Table 3
(4) ultralow line changes the performance of unburned air brick
The product prepared to embodiment 1-6, carry out apparent porosity, bulk density (GB/T2997-2000), the resistance to pressure of normal temperature Spend (GB/T5072-2008), strength at normal temperature (GB/T 3001-2007), thermal shock resistance (YB/T 376.1.2-1995), Six conventional performance index detections of permanent line change (GB/T 5988-2007) are heated, as a result such as table 4.
Table 4
Application examples
This product is used on Dalian Steel Plant 5#, 7#, 8#, 26#, 36#, 39#100 ton refining ladle stove, air penetrability is equal Reach 100%, volume stability is strong during showing product use, and service life is higher than existing product, uses rear residual brick thickness Higher than existing product, total refining time brings up to 2200min, substantially increases ladle running efficiency.Ultralow line change is unburned The service condition contrast with existing product of gas brick is shown in Table 5.
Table 5

Claims (10)

1. a kind of ultralow line changes unburned air brick, it is characterised in that is mixed by intermixture and additive；
Described intermixture forms as follows by weight percentage：
Described additive disperses water reducer by heat stabilizer, polycarboxylic acids and mineralizer forms, the addition of described heat stabilizer Measure as 0.01~0.03wt% of intermixture gross weight, the addition that described polycarboxylic acids disperses water reducer is intermixture gross weight 0.04~0.15wt%, the addition of described mineralizer is 0.01~0.03wt% of intermixture gross weight.
2. a kind of ultralow line according to claim 1 changes unburned air brick, it is characterised in that described sintering tabular is firm Beautiful particle, Al2O3Content >=98wt%, bulk density >=3.55g/cm3, granularity≤8mm, closed porosity 10~20%, 3~10um of aperture；Described corundum fine powder, Al2O3Content >=98wt%, granularity≤0.088mm.
3. a kind of ultralow line according to claim 1 changes unburned air brick, it is characterised in that described aluminium riched spinel Particle, MgO content 20~26wt%, Al2O372~79wt% of content, granularity≤8mm；Described aluminium riched spinel is micro- In powder, MgO content 20~26wt%, Al2O372~79wt% of content, meso-position radius D50 is 5~20um.
4. a kind of ultralow line according to claim 1 changes unburned air brick, it is characterised in that described active alpha-oxidation Aluminium micro mist, Al2O3Content >=98wt%, meso-position radius D50 is 0.5~6um.
5. a kind of ultralow line according to claim 1 changes unburned air brick, it is characterised in that described chrome oxide green is thin Powder, Cr2O3Content >=98wt%, granularity≤0.044mm.
6. a kind of ultralow line according to claim 1 changes unburned air brick, it is characterised in that described zirconium oxide is thin Powder, ZrO2Content >=90wt%, granularity≤0.044mm.
7. a kind of ultralow line according to claim 1 changes unburned air brick, it is characterised in that described pure calcium aluminate water Mud, Al2O3Content 68~71wt%, CaO 29~32wt% of content, granularity≤0.044mm.
8. a kind of ultralow line according to claim 1 changes unburned air brick, it is characterised in that described heat stabilizer is One or two or more kinds of mixing of SIS resins, C5 Petropols or calcium carbonate；It is grape that described polycarboxylic acids, which disperses water reducer, One or two or more kinds of mixing of sodium saccharate, lauryl sodium sulfate (K12), α-sodium olefin sulfonate (AOS)；Described mineralising Agent is one or two or more kinds of mixing of yittrium oxide, cerium oxide or nitroglycerin.
9. a kind of ultralow line described in claim 1 changes the preparation method of unburned air brick, it is characterised in that including following step Suddenly：
1) stocked up according to the proportioning described in claim 1；
2) first by corundum fine powder, aluminium riched spinel micro mist, pure calcium aluminate cement, powdered zirconium oxide, active alpha-alumina powder, poly- Carboxylic acid disperses water reducer and chrome oxide green fine powder mixes 3~5 minutes in premixing machine, obtains premixing flour, standby；
3) heat stabilizer and mineralizer are taken, heat stabilizer and the water of mineralizer gross weight 3~4% is added, stirs, it is standby；
4) sintering plate corundum particle and aluminium riched spinel particle are put into batch mixer, then add the premix that step 2) obtains Powder, dry-mixed 1~3 minute, the compound that step 3) obtains is eventually adding, uniform wet mixing 3~8 minutes, obtains castable；
5) castable for obtaining step 4) is added in mould, vibration moulding, and it is small that 12~48 are conserved under the conditions of 20~100 DEG C When, obtain base substrate；
6) base substrate after step 5) is molded is stripped, and is conserved 72~240 hours under the conditions of 20~100 DEG C, is obtained sample；
7) sample that step 6) obtains is heat-treated 12~48 hours under the conditions of 450~800 DEG C, a kind of ultralow line change is made Unburned air brick.
10. a kind of ultralow line described in claim 1 changes application of the unburned air brick in refining ladle air brick.
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CN112321305A (en) * 2020-11-06 2021-02-05 陈晓林 Multi-bubble ventilating element for refining steel ladle
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CN115417662A (en) * 2022-09-26 2022-12-02 武汉科技大学 Microporous corundum brick for hydrogen metallurgy and preparation method thereof

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